Mixed-wax, ethylene-vinyl acetate nonflaking coating composition



United States Patent 3,178,383 MIXED-WAX, ETHYLENE-VINYL ACETATE NQN- FLAKING COATING COMPOSITION William J. Stout, Wilmington, Del., assignor to Sun Gil glompany, Philadelphia, Pa., a corporation of New ersey No Drawing. Filed June 27, 1961, Ser. No. 119,793 7 Claims. (Cl. 260-28.5)

This invention relates to a novel wax composition. It particularly relates to a composition which is especially suitable for coating fibrous sheets and containers for packaging liquids. More particularly, it relates to a wax composition having superior non-flaking characteristics, being especially suitable for coating fibrous milk containers. Specifically, it relates to a wax composition containing a major proportion of a specific paraflin wax and minor proportions of a specific microcrystalline wax, another specific paraffin wax, and normally solid copolymer of ethylene and vinyl acetate. Additionally, the wax composition can contain a minor proportion of a specific distillate hydrocarbon oil.

This application is a continuation-in-part of my copending application Serial No. 59,500, filed September 30, 1960, now abandoned.

The use of wax to coat fibrous containers for use in packaging liquids is well known in the art. A particularly useful paraffin wax suitable for coating such containers is described and claimed in US. Patent No. 2,624,501. However, actual commercial use has disclosed several disadvantages of coatings formed from this wax. Such coatings on fibrous sheet material may develop minute imperfections which impart a serpentine efiect to the coating, thereby creating an unsightly appearance, and leakage of packaged liquid materials through the imperfections may develop. A further difficulty of this wax, as has been found, is the tendency of the coatings formed therefrom to fracture and break away from the fibrous material on suffering an impact so that wax flakes are present in the packaged liquid. Such flaking action of a wax is highly undesirable because the product is rendered objectionable to ultimate customers.

An object of the present invention is to provide a wax composition especially suitable for coating fibrous containers for fluids. A particular object is to provide a wax composition effective for coating paper containers for liquids which imparts a pleasing appearance to the resulting article of manufacture while obtaining good coverage and good blocking characteristics and which can be readily applied with conventional equipment. A specific object is to provide a wax composition which, when formed as a coating for a fibrous container, will not easily fracture on impact and will have substantially non-flaking characteristics.

The above and other objects can be obtained by blending the following components having specific properties in specific proportions: a relatively low melting paraffin wax, a relatively high melting paraflin wax, a microcrystalline wax having laminating properties, normally solid copolymer of ethylene and vinyl acetate, and optionally, a distillate hydrocarbon oil.

The components of the wax composition of the present invention are characterized as follows: As used herein, melting points are determined by ASTM D87-57, penetrations by ASTM D1321-'7T, and viscosities (SUS- Saybolt Universal Seconds) by ASTM D446-53. All percentages are weight percent.

WAX A This is a relatively low melt point paralfin wax. Typically, it has a melting point of from 125 F. to 132 F., a penetration (at 77 F.) of from 17 to 23, a viscosity ice (at 210 F.) of from 37 to 41 seconds, and a tensile strength at 40 F. of from 275 p.s.i. to 325 p.s.i., the the tensile strength at 40 F. being at least 25 psi, higher than the tensile strength at 70 F. This relatively low melt point parafiin wax may be prepared as follows: A slack wax from the dewaxing of lubricating oil, which may contain about 30% oil, is vacuum distilled and the fraction distilling between about 390 F. and 565 F. at 2 mm. of mercury pressure is collected. This fraction is dissolved in a solvent, preferably a mixture of methyl ethyl ketone and benzene in about equal volumes. Dissolution is performed at an elevated temperature, from about 165 F. to 195 F. being suitable, and advantageously about 6 parts by volume of solvent per part of wax is used. The solution is slowly cooled to a temperature of from F. to 83 F. and the wax which percipitates at this temperature is separated such as by filtration. The solution separated from the precipitated wax is further slowly cooled to a temperature of from 28 F. to 33 F. and the wax which precipitates at this temperature is separated and forms Wax A of the present composition. Preferably, the wax after separation from solution is washed, such as with the solvent employed for dissolution, preferably at the same temperature as used for filtration, namely from 28 F. to 32 F. and the wax is then separated.

An alternate method of preparing Wax A of the present invention which provides considerable flexibility in obtaining the desired wax product is to separate from slack wax two distillate fractions, one distilling under vacuum in the range of from about 390 F. to 475 F. at 2 mm. of mercury pressure and a second fraction distilling in the range of from about 450 F. to 565 F. at 2 mm. of mercury pressure. As usually occurs, the initial boiling point of the second fraction will overlap the end point of the first-mentioned distilled fraction. The lower boiling distillate fraction is dissolved in a solvent as above described and the solution is cooled to a temperature of from 25 F. to 31 F. The wax which precipitates at this temperature is separated as by filtering. The higher boiling distillate fraction is dissolved in a solvent as above described, except that a lower proportion of solvent to wax, say about 4.5 parts of solvent per part of wax, is advantageously used, and the solution is slowly cooled to a temperature of from 72 F. to 82 F. The wax which precipitates at this temperature is separated such as by filtering, and the remaining solution is further slowly cooled to a temperature of from 25 F. to 31 F. The wax which precipitates at this latter temperature is separated as by filtering and is mixed with the wax recovered from the lower boiling distillate fraction. This mixture of waxes is Wax A of the present invention. Considerable flexibility is obtained since the blending may be in various proportions so that the properties of the resulting wax mixture can be varied within the limits aboverlescribed for Wax A. If desired, the two waxes can be washed and dried prior to blending, or the wet waxes may be combined and simultaneously washed and then recovered by removal of the wash liquid. In general, from about 60 to 75% by weight of the parafiin wax will comprise wax from the lower boiling distillate fraction since, as has been found, such mixture gives a wax having properties within those defined for Wax A of the invention. It is preferred, however, that Wax A comprise 75% lower boiling distillate fraction and 25% higher boiling distillate fraction.

WAXB

This is a relatively high melt point paraflin wax. Typically, it has a melting point of from 148 F. to 154 F., a penetration (at F.) of from 13 to 19, and .a viscosity (at 210 F.) of from 40 to 46 seconds. This relatively high melt point paratlin wax can be prepared as follows: A slack wax from the dewaxing of lubricating oil or from topping a high wax content crude oil is distilled under vacuum, and the fraction distilling in the range of from about 450 F. to 565 F. at 2 mm. of mercury pressure is collected. The distillate fraction is dissolved in a solvent which is preferably a mixture of methyl ethyl ketone and benzene in about equal parts by volume, dissolution advantageously being at a temperature of from about 165 F. to 190 F. as above described, using about 2 parts of solvent per part of wax. The solution is slowly cooled to a temperature of from about 77 F. to 83 F. and the wax precipitated at this temperature is separated. The separated wax is Washed such as with the solvent employed for dissolution, preferably at the same temperature as used for filtration, and the wax is recovered. This wax form Wax B of the present invention.

WAX C This is a microcrystalline wax having laminating properties. Typically, it has a penetration (at 110 F.) of from 60 to 80, preferably 69 to 75, a viscosity (at 210 F.) of from 70 to 79, and an adhesion value of from 30 to 120, preferably between 65 and 85. The Wax C may be obtained by any of the methods known to the art. One especially suitable method is described and claimed in US. Patent No. 2,783,183. In general, the method of obtaining microcrystalline wax with laminating quality is as follows: A slack wax having from about 20 percent to about 50 percent oil is subjected to vacuum distillation to form a plurality of fractions. The desired fraction is dissolved in a hot solvent, such as a mixture of methyl ethyl ketone and benezene, chilled at one desired temperature and the precipitated wax separated by say, filtration. The filtrate from this first stsep is further chilled to another desired lower temperature, and the precipitated wax separated and recovered. This sequence is repeated until the desired wax fraction is obtained.

For example, a microcrystalline wax suitable for use in the composition of this invention is prepared as follows: Slack wax containing about 30 percent oil, obtained from the dewaxing of lubricating oils, is continuously vacuum distilled at 650 F. into two distillate fractions, one being removed at about 420 F. at 6 mm. mercury pressure, and the other at about 590 F. at 25 mm. mercury pressure. These low boiling fractions constitute 68 percent of the total charge. The high boiling residual fraction constitutes 32 percent of the total charge and is used for the recovery of the desired microcrystalline wax. This high boiling residual fraction is dissolved in 3.5 parts of a hot (150 F.) solvent mixture comprising 53 percent methyl ethyl ketone and 47 percent benzene. The resulting wax solution is cooled to 93 F., diluted with 5.5 parts of solvent, filtered (or centrifuged) to remove the precipitated wax, and the wax is washed with 4 parts of solvent. The filtrate from the initial filtrations is further cooled to 58 F., diluted with 6 parts of solvent, filtered, and washed with 4 parts of solvent. The wax product finally obtained, after solvent removal, has an adhesion value between 30 and 120 grams pull per 2 inch width and is designated herein as Wax C.

DISTILLATE OIL It is desirable in the preparation of the composition of the invention to use a distillate petroleum oil. This oil can be of naphthenic, parafiinic, or aromatic base stock. The oil, generally, will have an API gravity at 60 F. of from about 10.0 to 35.0, a viscosity at 100 F. of from 70 to 3500 seconds and a pour point up to +65 F., maximum. Preferably, a solvent refined, parafiinic base, petroleum distillate having a maximum pour point of F. is employed. The zero pour point limitation is preferable in order to prevent the introduction of relatively soft waxes or soft. wax-like materials which, if present,

may deleteriously affect the properties of the wax composition. Such solvent refined oil will have an API gravity at 60 F. of from 27.5 to 33, a vissocity at F. of 100 to 650 seconds, and a 0 F. pour point. This oil is designated herein as Oil P.

COPOLYMER As used herein, the normally solid copolymer of ethylene and vinyl acetate is designated as PEVA. The preparation of this copolymer, known in the art as a resin, is well known. This preparation involves copolymerizing a mixture of ethylene and vinyl acetate by means of a free radical producing catalyst such as oxygen or an organic peroxide, e.g., 5-butyl hydroperoxide, at a pressure of 100-200 atmosphere and a temperature of the order of C. to 250 C., and then flashing oflf the unreacted monomers from the solid resin. The proportion of ethylene to vinyl acetate in the resin can be varied considerably, but for the present invention, the PEVA should contain from 5 to 15 moles of ethylene per mole of vinyl acetate. Typically, PEVA contains 75.8% carbon, 12.0% hydrogen, and 12.2% oxygen; has a saponification number of about 219, and has a molecular weight of about 20,000. This copolymer, prepared in the foregoing manner, is a tough, resilient, and colorless resin which can be extruded or molded at elevated temperatures.

The above-specified components in specific combination make up the wax composition of the present invention. The incorporation of these components into the wax composition can be by any convenient means, such as by blending the waxes in molten state, together with the oil and polymer, to obtain a homogeneous blend.

The solvent designated in the methods of preparing the wax components may be any of the known dewaxing and deoiling solvents. The preferred solvent is a mixture of methyl ethyl ketone and benzene. Either of the components of the solvent may be replaced, however, in whole or in part, by other ketones, such as methyl butyl ketone or acetone, or hydrocarbons or halogenated hydrocarbons such as ethylene dichloride, pentane, and hexane, or alcohols such as propyl or the heptyl alcohols.

The adhesion test used herein for the microcrystalline wax component is performed as follows: Two strips of glassine paper, 2 inches by 6 inches, are laminated with the wax under test by pressing them mildly on a hot plate at a temperature just above the melting point of the wax. The load is adjusted to about 8 pounds of wax per ream of laminate, evenly distributed between the strips. This laminate is held at 73 F. in an atmosphere of 50 percent relative humidity for one hour before testing. Adhesion is the grams pull per 2 inch Width required to separate the strips by peeling.

Laminating waxes of the microcrystalline type will have adhesion values, measured as described above, offrom 30 to 120. Typical samples of microcrystalline waxes were tested and the following adhesion values were obtained: 35, 49, 59, 62, 74, 84, 89, 99, and 117.

The Tinius-Olsen angle of fracture test used herein to evaluate the flaking properties of waxes is performed on the Tinius-Olsen Stiffness Tester which has a six pound capacity. The procedure is as follows: Wax is formed into strips of specified dimensions (016 inch thick by 0.5 inch wide by 2 inches long) by solidifying molten wax on the surface of water to form the desired thickness, and cutting to the other dimensions. These wax strips are placed in the Tinius-Olsen Stiffness Tester and are evaluated for angle of fracture at 73 F. and at 36 F. This angle of fracture as measured by this apparatus is the angle at which the specimen fractures. Thus, it is desirable to formulate a wax composition which will, under test, fracture at a high angle of deformation. An angle of 78 is usually the maximum deformation that. can be measured on this instrument, although an angle of 90 is theoretically possible. Consequently, as used herein,

an angle measurement of 78 should be interpreted as 78.+.

The angle of fracture values at 73 F. and 36 F. are necessary for complete definition of flaking properties of the specimen. However, the angle of fracture at 36 F. is the critical value because this temperature corresponds approximately to the refrigeration temperature to which, say, milk cartons are exposed. The flaking characteristics are evaluated by determining the grams of Wax which flake ofi per 1000 milk cartons of one quart size, after subjecting the milk cartons to the standard drop test. Accordingly, the amount of flaking has been correlated with the angle of fracture at 36 F. as follows:

36 F. angle of Actual experience has shown that a wax composition with substantially non-flaking characteristics must have a minimum angle of fracture at 36 F. of 11 minimum, and at 73 F., 20 minimum. The wax composition of the present invention must have Tinius-Olsen angles of fracture within these latter specified values. On the other hand, the commercially available waxes of the art, such as the wax described in U.S. Patent No. 2,524,501, will have an angle of fracture at 36 F. of about 7 which represents about 50 grams of wax flaking per 1000 milk cartons of one quart size.

Non-flaking as used herein is a term which is applicable to wax compositions which result in wax flaking from 0 to 14 grams of wax per 1000 milk cartons of one quart size. More particularly, non-flaking is applicable to wax compositions having a Tinius-Olsen angle of fracture at 36 F. of from 11 to 78+ and at 73 F. of from It is essential for purposes of the present invention that the components be combined in amounts within the following specified ranges:

Concentration range,

Component: percent An excellent example of the Wax composition of the invention is a blend of:

Percent Wax A I 62 Wax B 20 Wax C 15 Oil 2 Copolymer 1 The above wax composition had an angle of fracture at 36 F. of 18 and at 73 F. of 24 which according to the above correlation is equivalent to essentially no wax flaking (approximately 1-2 grams) per 1000 milk cartons.

As used herein, a wax composition designated either expressly or by omission as containing zero oil content A commercially available copolymer (PEVA) having a mole ratio of ethylene to vinyl acetate of 8 to 1 was blended into molten Wax A. Upon solidifying and testing the following results were obtained:

Angle of Fracture Wax A PEVA It is noted that PEVA has essentially no effect on the low temperature flaking characteristics of paraffin wax. The benefit obtained at 73 F. (increase from 7 to 11) is of no practical value when the composition is used to coat milk containers which are refrigerated at approximately 36 F.

Example 2 The following blends illustrate the fact that the copolymer (PEVA), plus a laminating microcrystalline wax (Wax C) blended with Wax A does not produce a sub stantially non-flaking wax.

Angle of Fracture Wax A PEVA Wax C By comparing with Example 1, it is noticed that the microcrystalline wax component tends to increase the 73 F.

angle of fracture and tends to raise the 36 F. angle of fracture.

Example 3 These blends indicate that a higher melt point paraffin wax (Wax B) is necessary before a substantially non-flaking wax is produced.

Angle of Fracture Wax A PEVA Wax C Wax B 73 F. l 36 F.

The latter blend is an excellent non-flaking wax composition.

Example 4 The Wax compositions of Example 3 were reformulated by adding Oil P thereto. A petroleum oil having a viscosity of 500 SUS at 100 F., 29.6 API, and 0 F. pour point was blended into a mixture of Wax A, Wax B, Wax

7 C, and the PEVA having an 8' to l ethylene to vinyl acetate ratio with the following results:

It is noted that all bends are of satisfactory non-flaking quality. By comparing Example 3 with Example 4,- it is noted that by increasing PEVA contentfrom 2% to 4% in the absence of oil increased the 36 F. angle of fracture by 8 numbers whereas in Example 4 increasing PEVA' from 2% to 4% in the presence of oil decreased the 36 F. angle of fracture by 2 numbers. Orr the'oth'er hand, at the 1% PEVA level, the presence of oil increased the 36 F; angle-of fracture from 11 to 18.

The data in Examples 3' and 4 clearly indicate that the use of oil is not'essentialf'or formulating a wax With-nonflaking properties; Those skilled inthe alt will use oil according to the dictates of thefinal product which is coated with the composition of the'fireseiit invention.

Example 5 The following blend indicates that the presence of the copolymer is necessary to provide'the benefits of the wax composition of the invention. The 2% Oil P blend from Example 4 was reformulated without PEVA.

Angle of Fracture Wax A PEVA Wax O War B Oil P The above wax composition does not have the requisite angle of fracture values and is, therefore, unsatisfactory as a non-flaking wax composition. Thus, it is concluded that the copolymer is an essential component of the wax composition of the present invention.

Example 6 As hereinabove described, Wax A, prepared by said alternate method, is a blend of two distillate wax fractions. As specified, Wax A, in general, will consist of from 60% to 75% by weight of the lower boiling distillate fraction. The following blends indicate'the' effect on flaking characteristics of varying the composition of Wax A:

It is noted that the composition of Wax A can vary between 60% and 75 of the low boilingcomponent if the final composition contains at least 15% Wax C. For blends containing only 10% Wax C, it is necessary to' have Wax A composed of 70% to 75% of the low boiling distillate fraction in order to produce a wax composition having satisfactory non-flaking properties. Note also that each blend except the last one is an excellent non-flaking Wax composition.

In the above examples, Wax C has been shown in amounts of 10% to 15% of the blend. Actually, Wax C can be present in amounts ranging up to about 50% stick or adhere to the packaging equipment.

8 without atfecting the Tinius-Olsen values of the blend. However, it has been found that a composition of thepres'erit invention containing greater than Wax C when used to coatmills cartons causes the cartons to' Thus, the non-flaking wax compositions of the present invention should contain no more than 30% Wax C in order to be commercially acceptable.-

From the above data, a wax composition having nonfiaking characteristics will comprise essentially from 40% to 84.5% of relatively low melt-point wax having a melt point between 125 F. and 132 F., viscosity at 210 F. of between 37 and 41- seconds, and a tensile strength at 40 F. of from 275 p.s.i. to 325 p.s.i., the tensile strength-at 40% F. being at least 25 p.s.i. higher'th'an the con't'aining5 to 15 moles" of ethyl'eheper' mole of vinyl" This wax'compositiori will have aTinius-Olseii' acetate; angle of fracture at 36 F. of at least 11 and at 73 F. of atl'east" 20. Further, the above wax composition may have additionally the equivalent of from 05% to 3% hyd'reenuen' oil having an API gravity at of from 10.0 to 35.0, viscosity at 100 F. of fro'ni'70 to 3500 seconds, and a p'our point up to F.

On storing wax slabs preparedfrom" the compositions of the present invention for long periods of time under ambient temperature conditions, which includes a temperature of about F., no blocking of the slabs is observed.

The present wax composition is primarily intended for use in coating' fibrous fluid containers, particularly cardboard milk containers, which may be advantageously ac complished'by dipping of spraying the containers in or with molten wax. The present wax composition may be used in many other applications, especially where high tensile strength and low temperature flexibility and adhere'nceis desirable, such as in the coating of metal fluid containers, cafivas' impregnation, coating pa er drinking cups, etcl Furthermore, it is rec'o'ghize'dthat the" wax composition of the present invention may have added thereto various additives, such as anti-oxidants in amounts rang 210 F. of between 37 and 41 seconds, and a tensile strength at 40% F. of from 275 p.s.i. to 3:25 p.s.i., the tensilestrength at 40 F. being at least 25 p.s.i. higher than the tensile strength at 70 F.; from 5% to 25% relatively high melt pointparaffin Wax having a melt point between 148 F. and 1 54 F., viscosity at 210}? of from 40 to 46 seconds, and a penetration at F. of from 13 to 19; from 10% to 30% rn icrocrystallinewax having a penetration at F. of from 60 to 80, aviscosity at 210 F. of from 70 to 79 seconds, and an adhesion value of from 30 to and from 0.5% to 5% ofth'e" normally solid'copol'ymer of ethylene and vinyl acetate containing 5 to 15 moles of ethylene per mole of vinyl acetate; said wax composition having a Tinius-Olsen angle of fracture at 36 F. of at least 11 and at 73 F. of at-least 20.

2. Wax composition'according to claim 1 wherein said 9 normally solid copolymer contains 7 to 9 moles of ethylene per mole of vinyl acetate.

3. A container for packaging milk formed from fibrous sheet material and provided with an adherent non-flaking moisture resistant coating, said coating being a hydrocarbon composition comprising essentially from 40% to 84.5% of relatively low melt point parafiin wax having a melt point between 125 F. and 132 F., viscosity at 210 F. of from 37 to 41 seconds, and a tensile strength at 40 F. of from 275 p.s.i. to 325 p.s.i., the tensile strength at 40 F. being at least 25 p.s.i. higher than the tensile strength at 70 F.; from to 25% relatively high melt point paraffin wax having a melt point between 148 F. and 154 F., viscosity at 210 F. of from 40 to 46 seconds, and a penetration at 100 F. of from 13 to 19; from 10% to 30% microcrystalline wax having a penetr-ation at 110 F. of from 60 to 80, a viscosity at 210 F. of from 70 to 79 seconds, and an adhesion value of from 30 to 120; and from 0.5% to 5% of the normally solid copolymer of ethylene and vinyl acetate; said composition having a Tinius-Olsen angle of fracture at 36 F. of at least 11 and at 73 F. of at least 20.

4. A container according to claim 3 wherein the said normally solid copolymer of ethylene and vinyl acetate component of the said coating composition contains 7 to 9 moles of ethylene per mole of vinyl acetate.

5. Wax composition according to claim 1 wherein the amount of said normally solid copolymer is from 2 to 4%.

6. A wax composition with non-flaking characteristics comprising 53-70% relatively low melt point parafiin wax having a melt point between 125 F. and 132 F., viscosity at 210 F. of from 37 to 41 seconds, and a tensile strength at F. of from 275 p.s.i. to 325 p.s.i., the tensile strength at 40 F. being at least 25 p.s.i. higher than the tensile strength at 70 F.; 10-20% laminating microcrystalline wax having a penetration at 110 F. of from to 80, a viscosity at 210 of from to 79 seconds, and an adhesion value of from 30 to 120; 15-25% relatively high melt point paraffin wax having a melt point between 148 F. and 154 F, viscosity at 210 F. of from to 46 seconds, and a penetration at F. of from 13 to 19; 0-3% hydrocarbon oil having a viscosity at 100 F. of from 100-650 seconds, and 2-4% of the normally solid copolymer of ethylene and vinyl acetate containing 7-9 moles of ethylene per mol of vinyl acetate; said wax composition having a Tinius-Olsen angle of fracture at 36 F. of from 11-24 and at 73 F. of from 20 to 78.

7. A container according to claim 6 wherein said composition contains additionally from 0.5% to 3.0% hydrocarbon oil having a viscosity at 100 F. of from 70 to 3500 seconds.

References Cited by the Examiner UNITED STATES PATENTS 2,877,196 3/59 Reding 26028.5 2,988,528 6/61 Tench et a1. 260-285 MORRIS LIEBMAN, Primary Examiner.

MILTON STEARMAN, Examiner. 

1. A WAX COMPOSITION COMPRISING ESSENTIALLY FROM 40% TO 84.5% OF RELATIVELY LOW MELT POINT PARAFFIN WAX HAVNG A MELT POINT BETWEEN 125*F. AND 132*F., VISCOSITY AT 210*F. OF BETWEEN 37 AND 41 SECONDS, AND A TENSILE STRENGTH AT 40%F. OF FROM 275 P.S.I. TO 325 P.S.I., THE TENSILE STRENGTH AT 40*F. BEING AT LEAST 25 P.S.I. HIGHER THAN THE TENSILE STRENGTH AT 70*F.; FROM 5% TO 25% RELATIVELY HIGH MELT POINT PARAFFIN WAX HAVING A MELT POINT BETWEEN 148*F. AND 154*F., VISCOSITY AT 210*F. OF FROM 40 TO 46 SECONDS, AND A PENETRATION AT 100* F. OF FROM 13 TO 19; FROM 10% TO 30% MICROCRYSTALLINE WAX HAVING A PENETRATION AT 100*F. OF FROM 60 TO 80, A VISCOSITY AT 210*F. OF FROM 70 TO 79 SECONDS, AND AN ADHESION VALUE OF FROM 30 TO 120; AND FROM 0.5% TO 5% OF THE NORMALLY SOLID COPOLYMER OF ETHYLENE AND VINYL ACETATE CONTAINING 5 TO 15 MOLES OF ETHYLENE PER MOLE OF VINYL ACETATE; SAID WAX COMPOSITION HAVING A TINIUS-OLSEN ANGLE OF FRACTURE AT 36*F. OF AT LEAST 11* AND AT 73*F. OF AT LEAST 20*. 